Achieving 1,4-Additions to 'Impossible' Substrates

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There are no examples of catalytic aymmetric 1,4-additions of Grignard reagents (RMgX) to unsaturated amides (Case 1) despite the high synthetic utility that this transformation would offer. Similarly, no catalytic addition of a diorganozinc species (ZnR2) to an unsaturated esters (Case 2) has ever been reported. In collaboration with DowPharma we have recently uncovered the first examples of these two transformations. We wish to carry out a highly focused proof of application study for these remarkable reactions.